EP1949963A1 - Process for the flotation of non-sulfidic minerals and ores - Google Patents
Process for the flotation of non-sulfidic minerals and ores Download PDFInfo
- Publication number
- EP1949963A1 EP1949963A1 EP07001677A EP07001677A EP1949963A1 EP 1949963 A1 EP1949963 A1 EP 1949963A1 EP 07001677 A EP07001677 A EP 07001677A EP 07001677 A EP07001677 A EP 07001677A EP 1949963 A1 EP1949963 A1 EP 1949963A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- flotation
- ores
- collectors
- minerals
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005188 flotation Methods 0.000 title claims abstract description 55
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 55
- 239000011707 mineral Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 239000006260 foam Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002763 monocarboxylic acids Chemical class 0.000 claims abstract description 5
- 230000006872 improvement Effects 0.000 claims abstract description 3
- -1 hydroxyethyl radical Chemical group 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 229910021532 Calcite Inorganic materials 0.000 claims description 13
- 238000009291 froth flotation Methods 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 18
- 150000004665 fatty acids Chemical class 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 150000001412 amines Chemical class 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000003093 cationic surfactant Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 150000004760 silicates Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002168 alkylating agent Substances 0.000 description 4
- 229940100198 alkylating agent Drugs 0.000 description 4
- 125000005263 alkylenediamine group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003925 fat Substances 0.000 description 4
- 235000019197 fats Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920001353 Dextrin Polymers 0.000 description 3
- 239000004375 Dextrin Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 235000019425 dextrin Nutrition 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002563 ionic surfactant Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- IAIHUHQCLTYTSF-UHFFFAOYSA-N 2,2,4-trimethylbicyclo[2.2.1]heptan-3-ol Chemical compound C1CC2(C)C(O)C(C)(C)C1C2 IAIHUHQCLTYTSF-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- YVBCULSIZWMTFY-UHFFFAOYSA-N 4-Heptanol Natural products CCCC(O)CCC YVBCULSIZWMTFY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 244000303965 Cyamopsis psoralioides Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- SIOLDWZBFABPJU-UHFFFAOYSA-N isotridecanoic acid Chemical compound CC(C)CCCCCCCCCC(O)=O SIOLDWZBFABPJU-UHFFFAOYSA-N 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 150000003139 primary aliphatic amines Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005549 size reduction Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 229930006727 (-)-endo-fenchol Natural products 0.000 description 1
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- CUXYLFPMQMFGPL-WPOADVJFSA-N (9Z,11E,13E)-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C/CCCCCCCC(O)=O CUXYLFPMQMFGPL-WPOADVJFSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- WEEGYLXZBRQIMU-UHFFFAOYSA-N 1,8-cineole Natural products C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- YSTPAHQEHQSRJD-UHFFFAOYSA-N 3-Carvomenthenone Chemical compound CC(C)C1CCC(C)=CC1=O YSTPAHQEHQSRJD-UHFFFAOYSA-N 0.000 description 1
- WTKWFNIIIXNTDO-UHFFFAOYSA-N 3-isocyanato-5-methyl-2-(trifluoromethyl)furan Chemical compound CC1=CC(N=C=O)=C(C(F)(F)F)O1 WTKWFNIIIXNTDO-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 108091005950 Azurite Proteins 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical class C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 239000004667 Diesterquat Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WEEGYLXZBRQIMU-WAAGHKOSSA-N Eucalyptol Chemical compound C1C[C@H]2CC[C@]1(C)OC2(C)C WEEGYLXZBRQIMU-WAAGHKOSSA-N 0.000 description 1
- PSMFFFUWSMZAPB-UHFFFAOYSA-N Eukalyptol Natural products C1CC2CCC1(C)COCC2(C)C PSMFFFUWSMZAPB-UHFFFAOYSA-N 0.000 description 1
- 240000006927 Foeniculum vulgare Species 0.000 description 1
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004666 Monoesterquat Substances 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 102000015636 Oligopeptides Human genes 0.000 description 1
- 108010038807 Oligopeptides Proteins 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000017343 Quebracho blanco Nutrition 0.000 description 1
- 241000065615 Schinopsis balansae Species 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical group 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 229910052614 beryl Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 description 1
- RFFOTVCVTJUTAD-UHFFFAOYSA-N cineole Natural products C1CC2(C)CCC1(C(C)C)O2 RFFOTVCVTJUTAD-UHFFFAOYSA-N 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- VPNOHCYAOXWMAR-UHFFFAOYSA-N docosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCN VPNOHCYAOXWMAR-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 229910052864 hemimorphite Inorganic materials 0.000 description 1
- SHVBTTRUEDMJTK-UHFFFAOYSA-N hexadec-1-en-1-amine Chemical compound CCCCCCCCCCCCCCC=CN SHVBTTRUEDMJTK-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229940049290 hydrogenated coco-glycerides Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- BUHXFUSLEBPCEB-UHFFFAOYSA-N icosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN BUHXFUSLEBPCEB-UHFFFAOYSA-N 0.000 description 1
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010443 kyanite Substances 0.000 description 1
- 229910052850 kyanite Inorganic materials 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 230000004130 lipolysis Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- WGNKXCMZCXHUHX-UHFFFAOYSA-N octadec-1-en-1-amine Chemical compound CCCCCCCCCCCCCCCCC=CN WGNKXCMZCXHUHX-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- CNVZJPUDSLNTQU-SEYXRHQNSA-N petroselinic acid Chemical compound CCCCCCCCCCC\C=C/CCCCC(O)=O CNVZJPUDSLNTQU-SEYXRHQNSA-N 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229930006968 piperitone Natural products 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000007056 transamidation reaction Methods 0.000 description 1
- GWBUNZLLLLDXMD-UHFFFAOYSA-H tricopper;dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[O-]C([O-])=O.[O-]C([O-])=O GWBUNZLLLLDXMD-UHFFFAOYSA-H 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
- B03D1/011—Quaternary ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/016—Macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
Definitions
- This invention relates to the flotation of non-sulfidic minerals and ores and more particularly the use of certain cationic surfactants as collectors in a froth flotation process.
- Flotation is a separation technique commonly used in the dressing of minerals and crude ores for separating valuable materials from the gangue.
- Non-sulfidic minerals and ores in the context of the present invention include, for example, calcite, apatite, fluorite, scheelite, baryta, iron oxides and other metal oxides, for example, the oxides of titanium and zirconium, and also certain silicates and aluminosilicates.
- the mineral or ore is normally first subjected to preliminary size-reduction, dry-ground, but preferably wet-ground and suspended in water.
- Collectors are then normally added, often in conjunction with frothers and, optionally, other auxiliary reagents such as regulators, depressors (deactivators) and/or activators, in order to facilitate separation of the valuable materials from the unwanted gangue constituents of the ore in the subsequent flotation process.
- auxiliary reagents such as regulators, depressors (deactivators) and/or activators, in order to facilitate separation of the valuable materials from the unwanted gangue constituents of the ore in the subsequent flotation process.
- These reagents are normally allowed to act on the finely ground ore for a certain time (conditioning) before air is blown into the suspension (flotation) to produce a froth at its surface.
- the collector hydrophobicizes the surface of the minerals so that they adhere to the gas bubbles formed during the activation step.
- the valuable constituents are selectively hydrophobicized so that the unwanted constituents of the mineral or ore do not adhere to the gas bubbles.
- Surfactants and, in particular, anionic, cationic and ampholytic surfactants are used as collectors in the flotation-based dressing of minerals and ores, in particular of calcite which is of considerable value especially for the paper industry.
- Calcite represents an important filler with the ability for adjusting the whiteness and transparency of the paper.
- Calcite minerals are often accompanied by silicates so that, to purify the calcite, the silicate - which is undesirable for many applications - has to be removed.
- Another problem which has a serious impact on the selectivity of the froth flotation process is related to the magnesium content of the minerals or ores. Magnesium salts seriously improve the stability of the froth, which collapses slowly and therefore increases the flotation time, while the selectivity drops.
- an object of the present invention is to provide improved collectors which make flotation processes more economical, i.e. with which it is possible to obtain either greater yields of valuable material for the same quantities of collector and for the same selectivity or at least the same yields of valuable materials for reduced quantities of collector.
- a second object is to supply collectors which simultaneously meet the needs for high biodegradability.
- the present invention refers to a process for the flotation of non-sulfidic minerals or ores, in which crushed crude minerals or ores are mixed with water and a collector to form a suspension, air is introduced into the suspension in the presence of a reagent system and a floated foam containing said non-sulfidic minerals or ores formed therein along with a flotation residue comprising the gangue, wherein the improvement comprises using as the collector polymeric esterquats, obtainable by reacting alkanolamines with a mixture of monocarboxylic acids and dicarboxylic acids and quaternising the resulting esters in known manner, optionally after alkoxylation
- said polymeric esterquats are extremely effective as collectors for the flotation of non-sulfidic minerals and ores.
- the collectors according to the present invention have been found even more effective compared to the conventional mono/diesterquat mixture while exhibiting a similarly high degree of biodegradability.
- the products have been found rather useful for the separation of silicate minerals from calcite by froth flotation.
- the polymeric esterquats to be used as collectors according to the present invention represent known cationic surfactants which have so far been used as softeners for textiles and rinse conditioners for treating hair.
- the products are disclosed in detail, for example, in EP0770594 B1(Henkel ); the teaching of this reference is therefore incorporated by reference.
- the polymeric esterquats are obtained by reacting alkanol amines with a mixture of fatty acids and dicarboxylic acids and quaternising the resulting esters in known manner, optionally after alkoxylation.
- suitable polymeric esterquats are derived from alkanolamines are derived from amines following general formula (I).
- R 1 represents a hydroxyethyl radical
- R 2 and R 3 independently from each other stand for hydrogen, methyl or a hydroxyethyl radical.
- Typical examples are methyldiethanolamin (MDA), monoethanolamine (MES), diethanolamine (DEA) and triethanolamine (TEA).
- MDA methyldiethanolamin
- MES monoethanolamine
- DEA diethanolamine
- TAA triethanolamine
- triethanolamine is used as the starting material.
- Fatty acids in the context of the invention are understood to be aliphatic carboxylic acids corresponding to formula (II): R 4 COOH (II) in which R 4 CO is an aliphatic, linear or branched acyl radical containing 6 to 22 carbon atoms and 0 and/or 1, 2 or 3 double bonds.
- Typical examples are caproic acid, caprylic acid, 2-ethyl hexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and the technical mixtures thereof obtained, for example, in the pressure hydrolysis of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids.
- Technical fatty acids containing 12 to 18 carbon atoms for example, coconut oil, palm oil, palm kernel oil or tallow fatty acids, preferably in hydrogenated or partially hydrogenated form, are preferred.
- Dicarboxylic acids suitable for use as starting materials in accordance with the invention correspond to formula (III): HOOC-[X]-COOH (III) in which [X] stands for an optionally hydroxysubstituted saturated or unsaturated alk(en)ylene group containing 1 to 10 carbon atoms.
- Typical examples are succinic acid, maleic acid, glutaric acid, 1,12-dodecanedioic acid and, in particular, adipic acid.
- the fatty acids and the dicarboxylic acids may be used in a molar ratio of 1:10 to 10:1. However, it has proved to be of advantage to adjust a molar ratio of 1:4 to 1:6.
- the trialkanolamines on the one hand and the acids - i.e. fatty acids and dicarboxylic acids together - on the other hand may be used in a molar ratio of 1:1.3 to 1:2.4.
- a molar ratio of trialkanolamine to acids of 1:1.4 to 1:1.8 has proved to be optimal.
- the esterification may be carried out in known manner, for example as described in International patent application WO91/01295 (Henkel ).
- Suitable catalysts are hypophosphorous acids and alkali metal salts thereof, preferably sodium hypophosphite, which may be used in quantities of 0.01 to 0.1% by weight, and preferably in quantities of 0.05 to 0.07 % b.w. based on the starting materials.
- alkali metal and/or alkaline earth metal borohydrides for example potassium, magnesium and, in particular, sodium borohydride, as co-catalysts.
- co-catalysts are normally used in quantities of 50 to 1000 ppm, and more particularly in quantities of 100 to 500 ppm, again based on the starting materials.
- Corresponding processes are also the subject of DE4308792C1 and DE4409322 C1(Henkel ) to which reference is hereby specifically made. Mixtures of the fatty acids and dicarboxylic acids may be used or, alternatively, the esterification may be carried out with the two components in successive steps.
- Polymeric esterquats containing polyalkylene oxide may be produced by two methods.
- ethoxylated trialkanolamines may be used. This has the advantage that the distribution of alkylene oxide in the resulting esterquat is substantially the same in regard to the three OH groups of the amine.
- the preferred method is to alkoxylate the ester before quaternisation. This may be done in known manner, i.e. in the presence of basic catalysts and at elevated temperatures.
- Suitable catalysts are, for example, alkali metal and alkaline earth metal hydroxides and alcoholates, preferably sodium hydroxide, and more preferably, sodium methanolate.
- the catalysts are normally used in quantities of 0.5 to 5% by weight and preferably in quantities of 1 to 3% by weight, based on the starting materials. Where these catalysts are used, free hydroxyl groups are primarily alkoxylated. However, if calcined hydrotalcites or hydrotalcites hydrophobicized with fatty acids are used as catalysts, the alkylene oxides are also inserted into the ester bonds. This method is preferred where the required alkylene oxide distribution approaches that obtained where alkoxylated trialkanolamines are used. Ethylene and propylene oxide and mixtures thereof (random or block distribution) may be used as alkylene oxides. The reaction is normally carried out at temperatures in the range from 100 °C to 180 °C. The incorporation of, on average, 1 to 10 moles of alkylene oxide per mole of ester increases the hydrophilicity of the esterquat, improves solubility and reduces reactivity to anionic surfactants.
- the quaternisation of the fatty acid/dicarboxylic acid trialkanolamine esters may be carried out in known manner.
- the reaction with the alkylating agents may also be carried out in the absence of solvents, it is advisable to use at least small quantities of water or lower alcohols, preferably isopropyl alcohol, for the production of concentrates which have a solids content of at least 80% by weight, and more particularly, at least 90% by weight.
- Suitable alkylating agents are alkyl halides such as, for example, methyl chloride, dialkyl sulfates, such as dimethyl sulfate or diethyl sulphate, for example, or dialkyl carbonates, such as dimethyl carbonate or diethyl carbonate for example.
- the esters and the alkylating agents are normally used in a molar ratio of 1:0.95 to 1:1.05, i.e. in a substantially stoichiometric ratio.
- the reaction temperature is usually in the range from 40 °C to 80 °C, and more particularly, in the range from 50 °C to 60 °C.
- After the reaction it is advisable to destroy unreacted alkylating agent by addition of, for example, ammonia, an (alkanol)amine, an amino acid or an oligopeptide, as described for example in DE14026184A1 (Henkel ).
- quaternised alkanolamine-monoesters may be modified, adjust or even support the properties of the quaternised alkanolamine-monoesters by adding defined co-collectors such as, for example, cationic surfactants other than the quaternised alkanolamine-monoesters or amphotheric surfactants.
- defined co-collectors such as, for example, cationic surfactants other than the quaternised alkanolamine-monoesters or amphotheric surfactants.
- cationic surfactants are to be used as co-collectors in accordance with the invention, they may be selected in particular from
- the amine compounds mentioned above may be used as such or in the form of their water-soluble salts.
- the salts are obtained in given cases by neutralization which may be carried out both with equimolar quantities and also with more than or less than equimolar quantities of acid.
- Suitable acids are, for example, sulfuric acid, phosphoric acid, acetic acid and formic acid.
- ampholytic surfactants used as co-collectors in accordance with the invention are compounds which contain at least one anionic and one cationic group in the molecule, the anionic groups preferably consisting of sulfonic acid or carboxyl groups, and the cationic groups consisting of amino groups, preferably secondary or tertiary amino groups.
- Suitable ampholytic surfactants include, in particular,
- Said collectors and said co-collectors can be used in a weight ratio of about 10:90 to about 90:10, preferably about 25:75 to about 75:25, and most preferably about 40:60 to about 60:40.
- the collectors or, respectively, the mixtures of collectors and co-collectors must be used in a certain minimum quantity.
- a maximum quantity of collectors/co-collectors should not be exceeded, because otherwise frothing is too vigorous and selectivity with respect to the valuable minerals decreases.
- the quantities in which the collectors are be used in accordance with the invention are governed by the type of minerals or ores to be floated and by their valuable mineral content.
- the particular quantities required may vary within wide limits.
- the collectors and collector/co-collector mixtures according to the invention are used in quantities of from 50 to 2000 g/metric ton, and preferably in quantities of from 100 to 1500 g/metric ton of crude ore.
- Typical steps in the process sequence are, generally, firstly the dry or preferably wet grinding of the minerals or ores, suspension of the resulting ground mineral or ore in water in the presence of the flotation aids, and preferably after a contact time of the collectors and optionally co-collectors present in the flotation aids to be determined in each individual case, injection of air into the plant.
- the nature of the starting materials as well as the flotation aids is illustrated in more detail.
- Floatable minerals and ores may be divided into the two groups of polar and non-polar materials. Since non-polar minerals and ores are difficult to hydrate, these materials have to be classified as hydrophobic. Examples of non-polar minerals are graphite, molybdenite, diamond, coal and talcum which are all floatable in their naturally occurring state.
- polar minerals and ores have strong covalent or ionic surface bonds which are accesible to rapid hydration by water molecules in the form of multi-layers
- These starting materials include, for example, calcite, malachite, azurite, chrysocolla, wulfenite, cerrusite, whiterite, megnesite, dolomite, smithsonite, rhodochrosite, siderite, magnetite, monazite, hematite, goethite, chromite, pyrolusite, borax, wolframite, columbite, tantalite, rutile, zircon, hemimorphite, beryl, mica, biotite, quartz, feldspar, kyanite and garnet.
- the flotation of non-sulfidic, but polar minerals and ores is a preferred object of the present invention.
- the flotation behaviour of the individual mineral constituents can be controlled within certain limits through the particle size distribution of the ground mineral.
- the use of the collector or collector/co-collector mixture is also influenced by the particle size so that both particle size and, for example, collector concentration may be determined in situ in a brief series of tests.
- the particles have to be increasingly hydrophobicised with increasing particle size before flotation occurs.
- the ores should be so finely ground that the individual fine particles consist only of one type of mineral, namely either the valuable minerals or the impurities.
- the ideal particle size normally has to be determined in dependence upon the particular mineral.
- a particle size distribution of around 5 to 500 ⁇ m has generally been found to be practicable, narrower distributions being of advantage in some cases.
- silicate-rich ores can be separated by flotation with excellent results using the flotation aids according to the present invention, providing less than 40 % b.w., preferably less than 30 % b.w., and more preferably less than 15 % b.w. of the total mineral or ore fraction has particle sizes of less than 250 ⁇ m.
- % b.w. The lower limit to the particle sizes is determined both by the possibility of size reduction by machine and also by handling properties of the constituents removed by flotation.
- more than 20 % b.w. of the ground mineral or ore should be smaller than about 50 ⁇ m in size, a percentage of particles with this diameter of more than 30 or even 40 % b.w., for example, being preferred.
- the flotation aids may be used in only one separation step although, basically, they may even be used in several separation steps or in all necessary separation steps.
- the invention also encompasses the successive addition of several different flotation aids, in which case at least one or even more of the flotation aids must correspond to the invention.
- the fractions obtainable in this way may be further processes either together or even separately after the flotation process.
- the technical parameters of the flotation plant in conjunction with a certain flotation aid and a certain mineral or ore can influence the result of the flotation process within certain limits. For example, it can be of advantage to remove the froth formed after only a short flotation time because the content of floated impurities or floated valuable materials can change according to the flotation time. In this case, a relatively long flotation time can lead to a poorer result than a relatively short flotation time. Similarly, it can happen in the opposite case that the separation process leads to a greater purity or otherwise improved quality of the valuable-mineral fraction with increasing time. Optimising external parameters such as these is among the routine activities of the expert familiar with the technical specifications of the particular flotation machine.
- Reagents which modify surface tension or surface chemistry are generally used for flotation. They are normally classified as frothers, controllers, activators and depressants (deactivators), and of course (co-)collectors which already have been discussed above.
- Frothers support the formation of froth which guarantee collectors with an inadequate tendency to froth a sufficiently high froth density and a sufficiently long froth life to enable the laden froth to be completely removed.
- the use of the collectors or collector/co-collector systems mentioned above will eliminate the need to use other frothers. In special cases, however, it may necessary or at least advantageous - depending on the flotation process used - to regulate the frothing behaviour.
- suitable frothers are, for example, alcohols, more particularly aliphatic C 5 -C 8 alcohols such as, for example, n-pentanol, isoamyl alcohol, hexanol, heptanol, methylbutyl carbinol, capryl alcohol, 4-heptanol, which all have good frothing properties.
- Natural oils may also be used to support frothing.
- alcohols, ethers and ketones for example alpha-terpineol, borneol, fennel alcohol, piperitone, camphor, fenchol or 1,8-cineol, have both a collecting and a frothing effect.
- suitable frothers are non-ionic compounds, like, for example,. polypropylene glycol ethers.
- Depressants which may be effectively used for the purpose of the present invention include, for example, naturally occurring polysaccharides, such as guar, starch and cellulose. Quebracho, tannin, dextrin (white dextrin, British gum, and yellow dextrin) and other chemical derivatives may also be used, including in particular the derivatives of starch, guar and cellulose molecules of which the hydroxyl groups may be equipped with a broad range of anionic, cationic and non-ionic functions. Typical anionic derivatives are epoxypropyl trimethylammonium salts while methyl, hydroxyethyl and hydroxypropyl derivatives are mainly used as non-ionic compounds.
- the flotation aids according to the present invention may contain solvents in a quantity of 0.1 to 40 % b.w., preferably in a quantity of 1 to 30 % b.w., and most preferably in a quantity of 2 to 15 % b.w.
- Suitable solvents are, for example, the aliphatic alcohols mentioned above and other alcohols with shorter chain lengths.
- the flotation aids according to the present invention may contain small quantities of glycols, for example, ethylene glycol, propylene glycol or butylene glycol, and also monohydric linear or branched alcohols, for example, ethanol, n-propanol or isopropanol.
- Another object of the present invention is the use of polymeric esterquats as collectors for the froth flotation of non-sulfidic minerals or ores.
- the collectors to be used in accordance with the invention may be used with advantage in the dressing of such minerals or ores as quartz, kaolin, mica, phlogopite, feldspar, silicates and iron ores.
- the mixture was then cooled to 60 °C., the vacuum was broken by introduction of nitrogen, and 0.6 g of hydrogen peroxide was added in the form of a 30% by weight aqueous solution.
- the resulting ester was dissolved in 376 g of isopropyl alcohol, and 357 g (2.83 moles) of dimethyl sulfate were added to the resulting solution over a period of 1 hour at such a rate that the temperature did not rise above 65 °C.
- the mixture was stirred for another 2.5 h, the total nitrogen content being regularly checked by sampling. The reaction was terminated when constant total nitrogen content had been reached. A product with a solids content of 80 % b.w. was obtained.
- the collectors according to the present invention lead to a faster collapse of the foam compared to the state of the art which is desirable in the flotation of minerals and ores.
Abstract
Description
- This invention relates to the flotation of non-sulfidic minerals and ores and more particularly the use of certain cationic surfactants as collectors in a froth flotation process.
- Flotation is a separation technique commonly used in the dressing of minerals and crude ores for separating valuable materials from the gangue. Non-sulfidic minerals and ores in the context of the present invention include, for example, calcite, apatite, fluorite, scheelite, baryta, iron oxides and other metal oxides, for example, the oxides of titanium and zirconium, and also certain silicates and aluminosilicates. In dressing processes based on flotation, the mineral or ore is normally first subjected to preliminary size-reduction, dry-ground, but preferably wet-ground and suspended in water. Collectors are then normally added, often in conjunction with frothers and, optionally, other auxiliary reagents such as regulators, depressors (deactivators) and/or activators, in order to facilitate separation of the valuable materials from the unwanted gangue constituents of the ore in the subsequent flotation process. These reagents are normally allowed to act on the finely ground ore for a certain time (conditioning) before air is blown into the suspension (flotation) to produce a froth at its surface. The collector hydrophobicizes the surface of the minerals so that they adhere to the gas bubbles formed during the activation step. The valuable constituents are selectively hydrophobicized so that the unwanted constituents of the mineral or ore do not adhere to the gas bubbles. The valuable material-containing froth is stripped off and further processed. The object of flotation is to recover the valuable material of the minerals or ores in as high a yield as possible while at the same time obtaining a high enrichment level of the valuable mineral.
- Surfactants and, in particular, anionic, cationic and ampholytic surfactants are used as collectors in the flotation-based dressing of minerals and ores, in particular of calcite which is of considerable value especially for the paper industry. Calcite represents an important filler with the ability for adjusting the whiteness and transparency of the paper. Calcite minerals, however, are often accompanied by silicates so that, to purify the calcite, the silicate - which is undesirable for many applications - has to be removed. Another problem which has a serious impact on the selectivity of the froth flotation process is related to the magnesium content of the minerals or ores. Magnesium salts seriously improve the stability of the froth, which collapses slowly and therefore increases the flotation time, while the selectivity drops. In order to overcome the disadvantages known from the state of the art, for example, International patent application
WO 97/026995 (Henkel - Accordingly, an object of the present invention is to provide improved collectors which make flotation processes more economical, i.e. with which it is possible to obtain either greater yields of valuable material for the same quantities of collector and for the same selectivity or at least the same yields of valuable materials for reduced quantities of collector. A second object is to supply collectors which simultaneously meet the needs for high biodegradability.
- The present invention refers to a process for the flotation of non-sulfidic minerals or ores, in which crushed crude minerals or ores are mixed with water and a collector to form a suspension, air is introduced into the suspension in the presence of a reagent system and a floated foam containing said non-sulfidic minerals or ores formed therein along with a flotation residue comprising the gangue, wherein the improvement comprises using as the collector polymeric esterquats, obtainable by reacting alkanolamines with a mixture of monocarboxylic acids and dicarboxylic acids and quaternising the resulting esters in known manner, optionally after alkoxylation
- Surprisingly it has been observed that said polymeric esterquats are extremely effective as collectors for the flotation of non-sulfidic minerals and ores. In particular with respect to the presence of silicates and/or magnesium salts in the minerals or ores, the collectors according to the present invention have been found even more effective compared to the conventional mono/diesterquat mixture while exhibiting a similarly high degree of biodegradability. In particular, the products have been found rather useful for the separation of silicate minerals from calcite by froth flotation.
- The polymeric esterquats to be used as collectors according to the present invention represent known cationic surfactants which have so far been used as softeners for textiles and rinse conditioners for treating hair. The products are disclosed in detail, for example, in
EP0770594 B1(Henkel ); the teaching of this reference is therefore incorporated by reference. More particularly, the polymeric esterquats are obtained by reacting alkanol amines with a mixture of fatty acids and dicarboxylic acids and quaternising the resulting esters in known manner, optionally after alkoxylation. - According to the present invention, suitable polymeric esterquats are derived from alkanolamines are derived from amines following general formula (I).
- Fatty acids in the context of the invention are understood to be aliphatic carboxylic acids corresponding to formula (II):
R4COOH (II)
in which R4CO is an aliphatic, linear or branched acyl radical containing 6 to 22 carbon atoms and 0 and/or 1, 2 or 3 double bonds. Typical examples are caproic acid, caprylic acid, 2-ethyl hexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and the technical mixtures thereof obtained, for example, in the pressure hydrolysis of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids. Technical fatty acids containing 12 to 18 carbon atoms, for example, coconut oil, palm oil, palm kernel oil or tallow fatty acids, preferably in hydrogenated or partially hydrogenated form, are preferred. - Dicarboxylic acids suitable for use as starting materials in accordance with the invention correspond to formula (III):
HOOC-[X]-COOH (III)
in which [X] stands for an optionally hydroxysubstituted saturated or unsaturated alk(en)ylene group containing 1 to 10 carbon atoms. Typical examples are succinic acid, maleic acid, glutaric acid, 1,12-dodecanedioic acid and, in particular, adipic acid. - The fatty acids and the dicarboxylic acids may be used in a molar ratio of 1:10 to 10:1. However, it has proved to be of advantage to adjust a molar ratio of 1:4 to 1:6. The trialkanolamines on the one hand and the acids - i.e. fatty acids and dicarboxylic acids together - on the other hand may be used in a molar ratio of 1:1.3 to 1:2.4. A molar ratio of trialkanolamine to acids of 1:1.4 to 1:1.8 has proved to be optimal. The esterification may be carried out in known manner, for example as described in International patent application
WO91/01295 (Henkel DE4308792C1 andDE4409322 C1(Henkel ) to which reference is hereby specifically made. Mixtures of the fatty acids and dicarboxylic acids may be used or, alternatively, the esterification may be carried out with the two components in successive steps. - Polymeric esterquats containing polyalkylene oxide may be produced by two methods. First, ethoxylated trialkanolamines may be used. This has the advantage that the distribution of alkylene oxide in the resulting esterquat is substantially the same in regard to the three OH groups of the amine. However, it also has the disadvantage that the esterification reaction is more difficult to carry out on steric grounds. Accordingly, the preferred method is to alkoxylate the ester before quaternisation. This may be done in known manner, i.e. in the presence of basic catalysts and at elevated temperatures. Suitable catalysts are, for example, alkali metal and alkaline earth metal hydroxides and alcoholates, preferably sodium hydroxide, and more preferably, sodium methanolate. The catalysts are normally used in quantities of 0.5 to 5% by weight and preferably in quantities of 1 to 3% by weight, based on the starting materials. Where these catalysts are used, free hydroxyl groups are primarily alkoxylated. However, if calcined hydrotalcites or hydrotalcites hydrophobicized with fatty acids are used as catalysts, the alkylene oxides are also inserted into the ester bonds. This method is preferred where the required alkylene oxide distribution approaches that obtained where alkoxylated trialkanolamines are used. Ethylene and propylene oxide and mixtures thereof (random or block distribution) may be used as alkylene oxides. The reaction is normally carried out at temperatures in the range from 100 °C to 180 °C. The incorporation of, on average, 1 to 10 moles of alkylene oxide per mole of ester increases the hydrophilicity of the esterquat, improves solubility and reduces reactivity to anionic surfactants.
- The quaternisation of the fatty acid/dicarboxylic acid trialkanolamine esters may be carried out in known manner. Although the reaction with the alkylating agents may also be carried out in the absence of solvents, it is advisable to use at least small quantities of water or lower alcohols, preferably isopropyl alcohol, for the production of concentrates which have a solids content of at least 80% by weight, and more particularly, at least 90% by weight. Suitable alkylating agents are alkyl halides such as, for example, methyl chloride, dialkyl sulfates, such as dimethyl sulfate or diethyl sulphate, for example, or dialkyl carbonates, such as dimethyl carbonate or diethyl carbonate for example. The esters and the alkylating agents are normally used in a molar ratio of 1:0.95 to 1:1.05, i.e. in a substantially stoichiometric ratio. The reaction temperature is usually in the range from 40 °C to 80 °C, and more particularly, in the range from 50 °C to 60 °C. After the reaction it is advisable to destroy unreacted alkylating agent by addition of, for example, ammonia, an (alkanol)amine, an amino acid or an oligopeptide, as described for example in
DE14026184A1 (Henkel ). - In certain cases it may be advantageous to modify, adjust or even support the properties of the quaternised alkanolamine-monoesters by adding defined co-collectors such as, for example, cationic surfactants other than the quaternised alkanolamine-monoesters or amphotheric surfactants.
- Where cationic surfactants are to be used as co-collectors in accordance with the invention, they may be selected in particular from
- Primary aliphatic amines,
- Alkylenediamines substituted by alpha-branched alkyl radicals,
- Hydroxyalkyl-substituted alkylenediamines,
- Water-soluble acid addition salts of these amines,
- Quaternary ammonium compounds, and in particular
- Quaternised N,N-dialkylaminoalkylamines.
- Suitable primary aliphatic amines include, above all, the C8-C22 fatty amines derived from the fatty acids of natural fats and oils, for example n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, n-eicosylamine, n-docosylamine, n-hexadecenylamine and n-octadecenylamine. The amines mentioned may be individually used as co-collectors, although amine mixtures of which the alkyl and/or alkenyl radicals derive from the fatty acid component of fats and oils of animal or vegetable origin are normally used. It is known that amine mixtures such as these may be obtained from the fatty acids obtained by lipolysis from natural fats and oils via the associated nitriles by reduction with sodium and alcohols or by catalytic hydrogenation. Examples include tallow amines or hydrotallow amines of the type obtainable from tallow fatty acids or from hydrogenated tallow fatty acids via the corresponding nitriles and hydrogenation thereof.
- The alkyl-substituted alkylenediamines suitable for use as co-collectors correspond to formula (IV),
R6CHR7-NH-(CH2)nNH2 (IV)
in which R6 and R7 represent linear or branched alkyl or alkenyl radicals and in which n = 2 to 4. The production of these compounds and their use in flotation is described in East German PatentDD 64275 - The hydroxyalkyl-substituted alkylenediamines suitable for use as co-collectors correspond to formula (V),
- The amine compounds mentioned above may be used as such or in the form of their water-soluble salts. The salts are obtained in given cases by neutralization which may be carried out both with equimolar quantities and also with more than or less than equimolar quantities of acid. Suitable acids are, for example, sulfuric acid, phosphoric acid, acetic acid and formic acid.
- The quaternary ammonium compounds suitable for use as co-collectors correspond to formula (VI),
[R10R11R12R13N+] X- (VI)
in which R10 is preferably a linear alkyl radical containing 1 to 18 carbon atoms, R11 is an alkyl radical containing 1 to 18 carbon atoms or a benzyl radical, R12 and R13 may be the same or different and each represent an alkyl radical containing 1 to 2 carbon atoms, and X is a halide anion, particularly a chloride ion. In preferred quaternary ammonium compounds, R10 is an alkyl radical containing 8 to 18 carbon atoms; R11, R12 and R13 are the same and represent either methyl or ethyl groups; and X is a chloride ion. - The most preferred cationic co-collectors, however, encompass the group of quaternised N,N-dialkylaminoalkylamides corresponding preferably to formula (VII),
- The ampholytic surfactants used as co-collectors in accordance with the invention are compounds which contain at least one anionic and one cationic group in the molecule, the anionic groups preferably consisting of sulfonic acid or carboxyl groups, and the cationic groups consisting of amino groups, preferably secondary or tertiary amino groups. Suitable ampholytic surfactants include, in particular,
- Sarcosides,
- Taurides,
- N-substituted aminopropionic acids and
- N-(1,2-dicarboxyethyl)-N-alkylsulfosuccinamates.
- The sarcosides suitable for use as co-collectors correspond to formula (VIII),
- The taurides suitable for use as co-collectors correspond to formula (IX),
- N-substituted aminopropionic acids suitable for use as co-collectors correspond to formula (X),
R20(NHCH2CH2)nN+H2CH2CH2COO- (X)
in which n may be 0 or a number from 1 to 4, while R20 is an alkyl or acyl radical containing from 8 to 22 carbon atoms. The afore-mentioned N-substituted aminopropionic acids are also known compounds obtainable by known methods. Their use as collectors in flotation is described by H. Schubert, loc. cit. and in Int. J. Min. Proc.9 (1982), pp 353-384 . - The N-(1,2-dicarboxyethyl)-N-alkylsulfosuccinamates suitable for use as co-collectors according to the invention correspond to formula (XI),
- Said collectors and said co-collectors can be used in a weight ratio of about 10:90 to about 90:10, preferably about 25:75 to about 75:25, and most preferably about 40:60 to about 60:40. To obtain economically useful results in the flotation of non-sulfidic minerals or ores, the collectors or, respectively, the mixtures of collectors and co-collectors must be used in a certain minimum quantity. However, a maximum quantity of collectors/co-collectors should not be exceeded, because otherwise frothing is too vigorous and selectivity with respect to the valuable minerals decreases. The quantities in which the collectors are be used in accordance with the invention are governed by the type of minerals or ores to be floated and by their valuable mineral content. Accordingly, the particular quantities required may vary within wide limits. In general, the collectors and collector/co-collector mixtures according to the invention are used in quantities of from 50 to 2000 g/metric ton, and preferably in quantities of from 100 to 1500 g/metric ton of crude ore.
- Typical steps in the process sequence are, generally, firstly the dry or preferably wet grinding of the minerals or ores, suspension of the resulting ground mineral or ore in water in the presence of the flotation aids, and preferably after a contact time of the collectors and optionally co-collectors present in the flotation aids to be determined in each individual case, injection of air into the plant. In the following the nature of the starting materials as well as the flotation aids is illustrated in more detail.
- Floatable minerals and ores may be divided into the two groups of polar and non-polar materials. Since non-polar minerals and ores are difficult to hydrate, these materials have to be classified as hydrophobic. Examples of non-polar minerals are graphite, molybdenite, diamond, coal and talcum which are all floatable in their naturally occurring state. By contrast, polar minerals and ores have strong covalent or ionic surface bonds which are accesible to rapid hydration by water molecules in the form of multi-layers, These starting materials include, for example, calcite, malachite, azurite, chrysocolla, wulfenite, cerrusite, whiterite, megnesite, dolomite, smithsonite, rhodochrosite, siderite, magnetite, monazite, hematite, goethite, chromite, pyrolusite, borax, wolframite, columbite, tantalite, rutile, zircon, hemimorphite, beryl, mica, biotite, quartz, feldspar, kyanite and garnet. The flotation of non-sulfidic, but polar minerals and ores is a preferred object of the present invention.
- The flotation behaviour of the individual mineral constituents can be controlled within certain limits through the particle size distribution of the ground mineral. Conversely, however, the use of the collector or collector/co-collector mixture is also influenced by the particle size so that both particle size and, for example, collector concentration may be determined in situ in a brief series of tests. Generally, however, it may be said that the particles have to be increasingly hydrophobicised with increasing particle size before flotation occurs. As a general rule, the ores should be so finely ground that the individual fine particles consist only of one type of mineral, namely either the valuable minerals or the impurities. The ideal particle size normally has to be determined in dependence upon the particular mineral. In the present case, however, a particle size distribution of around 5 to 500 µm has generally been found to be practicable, narrower distributions being of advantage in some cases. For example, silicate-rich ores can be separated by flotation with excellent results using the flotation aids according to the present invention, providing less than 40 % b.w., preferably less than 30 % b.w., and more preferably less than 15 % b.w. of the total mineral or ore fraction has particle sizes of less than 250 µm. To enable the flotation process to be optimally carried out, it can be particularly preferred for the particles larger than 125 µm in size to make up less than 15 % b.w., or preferably less than 10 % b.w. or even 6 % b.w. The lower limit to the particle sizes is determined both by the possibility of size reduction by machine and also by handling properties of the constituents removed by flotation. In general, more than 20 % b.w. of the ground mineral or ore should be smaller than about 50 µm in size, a percentage of particles with this diameter of more than 30 or even 40 % b.w., for example, being preferred. According to the present invention it is of particular advantage for more than 40 % b.w. of the mineral or ore particles to be smaller than 45 µm in diameter.
- In certain cases, it may be necessary and appropriate to divide the ground material into two or more fractions, for example three, four or five fractions differing in their particle diameter and separately to subject these fractions to separation by flotation. According to the present invention, the flotation aids may be used in only one separation step although, basically, they may even be used in several separation steps or in all necessary separation steps. The invention also encompasses the successive addition of several different flotation aids, in which case at least one or even more of the flotation aids must correspond to the invention. The fractions obtainable in this way may be further processes either together or even separately after the flotation process.
- The technical parameters of the flotation plant in conjunction with a certain flotation aid and a certain mineral or ore can influence the result of the flotation process within certain limits. For example, it can be of advantage to remove the froth formed after only a short flotation time because the content of floated impurities or floated valuable materials can change according to the flotation time. In this case, a relatively long flotation time can lead to a poorer result than a relatively short flotation time. Similarly, it can happen in the opposite case that the separation process leads to a greater purity or otherwise improved quality of the valuable-mineral fraction with increasing time. Optimising external parameters such as these is among the routine activities of the expert familiar with the technical specifications of the particular flotation machine.
- Reagents which modify surface tension or surface chemistry are generally used for flotation. They are normally classified as frothers, controllers, activators and depressants (deactivators), and of course (co-)collectors which already have been discussed above.
- Frothers support the formation of froth which guarantee collectors with an inadequate tendency to froth a sufficiently high froth density and a sufficiently long froth life to enable the laden froth to be completely removed. In general, the use of the collectors or collector/co-collector systems mentioned above will eliminate the need to use other frothers. In special cases, however, it may necessary or at least advantageous - depending on the flotation process used - to regulate the frothing behaviour. In this case, suitable frothers are, for example, alcohols, more particularly aliphatic C5-C8 alcohols such as, for example, n-pentanol, isoamyl alcohol, hexanol, heptanol, methylbutyl carbinol, capryl alcohol, 4-heptanol, which all have good frothing properties. Natural oils may also be used to support frothing. In particular, alcohols, ethers and ketones, for example alpha-terpineol, borneol, fennel alcohol, piperitone, camphor, fenchol or 1,8-cineol, have both a collecting and a frothing effect. Other suitable frothers are non-ionic compounds, like, for example,. polypropylene glycol ethers.
- Depressants which may be effectively used for the purpose of the present invention include, for example, naturally occurring polysaccharides, such as guar, starch and cellulose. Quebracho, tannin, dextrin (white dextrin, British gum, and yellow dextrin) and other chemical derivatives may also be used, including in particular the derivatives of starch, guar and cellulose molecules of which the hydroxyl groups may be equipped with a broad range of anionic, cationic and non-ionic functions. Typical anionic derivatives are epoxypropyl trimethylammonium salts while methyl, hydroxyethyl and hydroxypropyl derivatives are mainly used as non-ionic compounds.
- To adjust their rheological behaviour, the flotation aids according to the present invention may contain solvents in a quantity of 0.1 to 40 % b.w., preferably in a quantity of 1 to 30 % b.w., and most preferably in a quantity of 2 to 15 % b.w. Suitable solvents are, for example, the aliphatic alcohols mentioned above and other alcohols with shorter chain lengths. Thus the flotation aids according to the present invention may contain small quantities of glycols, for example, ethylene glycol, propylene glycol or butylene glycol, and also monohydric linear or branched alcohols, for example, ethanol, n-propanol or isopropanol.
- As outlined above, flotation is carried out under the same conditions as state-of-the-art processes. Reference in this regard is made to the following literature references on the background to ore preparation technology: H. Schubert, Aufbereitung fester mineralischer Stoffe (Dressing of Solid Mineral Raw Materials), Leipzig 1967 ; B. Wills, Mineral Processing Technology Plant Design, New York, 1978 ; D. B. Purchas (ed.), Solid/Liquid Separation Equipment Scale-up, Croydon 1977 ; E. S. Perry, C. J. van Oss, E. Grushka (ed.), Separation and Purification Methods, New York, 1973 to 1978 . As far as the process for conducting the froth flotation of non-sulfidic minerals and ores is concerned, their contents are incorporated by reference.
- Another object of the present invention is the use of polymeric esterquats as collectors for the froth flotation of non-sulfidic minerals or ores. The collectors to be used in accordance with the invention may be used with advantage in the dressing of such minerals or ores as quartz, kaolin, mica, phlogopite, feldspar, silicates and iron ores.
- 567 g (2.1 moles) of partly hydrogenated palm oil fatty acid, 219 g (1.5 moles) of adipic acid and 0.3 g of hypophosphoric acid were introduced into a stirred reactor and heated to 70 °C under a reduced pressure of 20 mbar. 447 g (3 moles) of triethanolamine were then added dropwise in portions and, at the same time, the temperature was increased to 120 °C. After the addition, the reaction mixture was heated to 160 °C, the pressure was reduced to 3 mbar and the mixture was stirred under those conditions for 2.5 h until the acid value had fallen to below 5 mg KOH/g. The mixture was then cooled to 60 °C., the vacuum was broken by introduction of nitrogen, and 0.6 g of hydrogen peroxide was added in the form of a 30% by weight aqueous solution. For the quaternisation step, the resulting ester was dissolved in 376 g of isopropyl alcohol, and 357 g (2.83 moles) of dimethyl sulfate were added to the resulting solution over a period of 1 hour at such a rate that the temperature did not rise above 65 °C. After the addition, the mixture was stirred for another 2.5 h, the total nitrogen content being regularly checked by sampling. The reaction was terminated when constant total nitrogen content had been reached. A product with a solids content of 80 % b.w. was obtained.
- The following examples demonstrate the superiority of the polymeric esterquats to be used in accordance with the invention over collector components known from the prior art, in particular compared to convention mono/di-esterquat mixtures. The tests were carried out under laboratory conditions, in some cases with increased collector concentrations considerably higher than necessary in practice. Accordingly, the potential applications and in-use conditions are not limited to separation exercises and test conditions described in the examples. The quantities indicated for reagents are all based on active substance.
- The following examples and comparative examples illustrate the effectiveness of the collectors according to the present invention compared to conventional mono/di-esterquat collectors in the flotation of silicate containing calcite minerals. The results are shown in Table 1.
Particle size distribution: > 40 µm: > 50 % b.w.
Silicates: about 1.5 to 2.5 % b.w.
Calcite: about 97.5 to 98.5 % b.w.Table 1 Calcite flotation Composition C1 C2 C3 1 2 3 Dehyquart® AU 461 [g*t-1] 660 560 320 - - - Dehyquart® 042 [g*t-1] - - - 350 300 250 OMC 63173 [g*t-1] 100 100 85 - - - Results Yield Floated Material [g] 39.8 75.4 59.7 40.3 80.3 64.8 Yield Residue [g] 383 361 438 401 438 525 Feed: HCl insoluble [%] 2.6 2.6 2.2 2.5 2.6 2.1 Floated Material : HCl insoluble [%] 25.7 13.6 18.4 45,7 49.0 50,7 Residue: HCl insoluble [%] 0.09 0.18 0.57 0.06 0.1 0.35 Calcite Loss [%] 7.2 15.3 10.0 2,9 2,6 1,7 - The following examples and comparative examples illustrate the effectiveness of the collectors according to the present invention compared to conventional mono/di-esterquat collectors under conditions of high magnesium concentrations. The foam height was measured according to the well known Ross-Miles method. The results are shown in Table 2:
Table 2 Foaming behaviour in the presence of magnesium chloride (AS = Active Substance) Ex. Product Addition AS [% b.w.] Quantity Product [g] Test Solution Foam height [ml] Foam half life [min] C4 Dehyquart® 1 2.25 2 % MgCl2 220 2:35 AU 46 2.29 2 % MgCl2 220 2:35 C5 Dehyquart® 1 2.27 5 % MgCl2 220 0:30 AU 46 2.54 5 % MgCl2 220 0:30 4 Dehyquart® 1 2.25 2 % MgCl2 220 2:05 AU 04 2.29 2 % MgCl2 220 2:05 5 Dehyquart® 1 2.27 5 % MgCl2 220 0:15 AU 04 2.54 5 % MgCl2 220 0:15 1 Methyl-quaternised Triethanolamine-mono/di-stearate, Methosulfate, 90 % b.w. AS (Cognis Iberia, ES)
2 Polymeric esterquat, 90 % b.w. AS (Cognis Iberia, ES) according to Manufacturing Example M1
3 Frother (Cognis Deutschland GmbH & Co. KG, DE) - As one can see, the collectors according to the present invention lead to a faster collapse of the foam compared to the state of the art which is desirable in the flotation of minerals and ores.
Claims (10)
- In a process for the flotation of non-sulfidic minerals or ores, in which crushed crude minerals or ores are mixed with water and a collector to form a suspension, air is introduced into the suspension in the presence of a reagent system and a floated foam containing said non-sulfidic minerals or ores formed therein along with a flotation residue comprising the gangue, wherein the improvement comprises using as the collector polymeric esterquats, obtainable by reacting alkanolamines with a mixture of monocarboxylic acids and dicarboxylic acids and quaternising the resulting esters in known manner, optionally after alkoxylation.
- Process according to Claims 1 and/or 2, characterised in that polymeric esterquats based on triethanolamine are used.
- Process according to any of Claims 1 to 3, characterised in that polymeric esterquats are used derived from mixtures of(i) Monocarboxylic acids according to general formula (II),
R4CO-OH (II)
in which R4CO stands for a linear or branched acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, and(ii) Dicarboxylic acids according to general formula (III),
HOOC-[X]-COOH (III)
in which [X] stands for an optionally hydroxysubstituted alk(en)ylene group having 1 to 10 carbon atoms. - Process according to any of Claims 1 to 4, characterised in that polymeric esterquats are used obtained from mixtures of monocarboxylic acids and dicarboxylic acids in a molar ratio of 1:10 to 10:1.
- Process according to any of Claims 1 to 5, characterised in that polymeric esterquats are used based on mixtures of C12-C22 fatty acids and adipic acid.
- Process according to any of Claims 1 to 6, characterised in that quaternised N,N-dialkylaminoalkylamides are used as co-collectors.
- Process according to Claim 7, characterised in that said collectors and said co-collectors are used in a weight ratio of 10:90 to 90:10.
- Use of polymeric esterquats according to Claim 1 as collectors for the froth flotation of non-sulfidic minerals or ores.
- Use according to Claim 9, characterised in that calcite minerals are subjected to said froth flotation.
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07001677.9A EP1949963B2 (en) | 2007-01-26 | 2007-01-26 | Use of polymeric esterquats for the flotation of non-sulfidic minerals and ores |
AT07001677T ATE483525T1 (en) | 2007-01-26 | 2007-01-26 | METHOD FOR FLOTATION OF NON-SULFIDIC MINERALS AND ORES |
ES07001677.9T ES2354119T5 (en) | 2007-01-26 | 2007-01-26 | Use of polymeric esterquats for flotation of minerals and non-sulphurous ores |
DE602007009632T DE602007009632D1 (en) | 2007-01-26 | 2007-01-26 | Process for the flotation of non-sulfidic minerals and ores |
CA2676741A CA2676741C (en) | 2007-01-26 | 2008-01-17 | Process for the separation of non-sulfidic minerals and ores from unwanted constituents of crude mineral and ore |
US14/790,635 USRE46235E1 (en) | 2007-01-26 | 2008-01-17 | Process for the separation of non-sulfidic minerals and ores from unwanted constituents of crude mineral and ore |
US12/524,710 US8474627B2 (en) | 2007-01-26 | 2008-01-17 | Process for the flotation of non-sulfidic minerals and ores |
PCT/EP2008/000309 WO2008089906A1 (en) | 2007-01-26 | 2008-01-17 | Process for the flotation of non-sulfidic minerals and ores |
NO20092889A NO337171B1 (en) | 2007-01-26 | 2009-08-24 | Use of polymeric ester quatrains as collecting agents for the foam flotation of non-sulfurous minerals or ore |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07001677.9A EP1949963B2 (en) | 2007-01-26 | 2007-01-26 | Use of polymeric esterquats for the flotation of non-sulfidic minerals and ores |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1949963A1 true EP1949963A1 (en) | 2008-07-30 |
EP1949963B1 EP1949963B1 (en) | 2010-10-06 |
EP1949963B2 EP1949963B2 (en) | 2014-04-02 |
Family
ID=38197942
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07001677.9A Active EP1949963B2 (en) | 2007-01-26 | 2007-01-26 | Use of polymeric esterquats for the flotation of non-sulfidic minerals and ores |
Country Status (8)
Country | Link |
---|---|
US (2) | US8474627B2 (en) |
EP (1) | EP1949963B2 (en) |
AT (1) | ATE483525T1 (en) |
CA (1) | CA2676741C (en) |
DE (1) | DE602007009632D1 (en) |
ES (1) | ES2354119T5 (en) |
NO (1) | NO337171B1 (en) |
WO (1) | WO2008089906A1 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011147855A2 (en) | 2010-05-28 | 2011-12-01 | Akzo Nobel Chemicals International B.V. | Quaternary ammonium compounds and their use as collectors in froth flotation processes |
WO2012028542A1 (en) | 2010-08-30 | 2012-03-08 | Akzo Nobel Chemicals International B.V. | Use of polyester polyamine and polyester polyquaternary ammonium compounds as corrosion inhibitors |
WO2015091308A1 (en) * | 2013-12-18 | 2015-06-25 | Akzo Nobel Chemicals International B.V. | Polyester polyquaternary ammonium compound collectors for reverse froth flotation of silicates from nonsulfidic ores |
US9228089B2 (en) | 2010-12-28 | 2016-01-05 | Akzo Nobel Chemicals International B.V. | Polyester polyamine and polyester polyquaternary ammonium corrosion inhibitors |
FR3047675A1 (en) * | 2016-02-16 | 2017-08-18 | Ceca Sa | |
FR3047674A1 (en) * | 2016-02-16 | 2017-08-18 | Ceca Sa | |
WO2020007773A1 (en) | 2018-07-03 | 2020-01-09 | Nouryon Chemicals International B.V. | Collector composition containing biodegradable compound and process for treating siliceous ores |
CN110947519A (en) * | 2019-12-31 | 2020-04-03 | 天津天宝翔科技有限公司 | Silicate mineral inhibitor and preparation method and application thereof |
CN113874118A (en) * | 2019-06-06 | 2021-12-31 | 巴斯夫欧洲公司 | Collectors for flotation processes |
WO2022243367A1 (en) | 2021-05-18 | 2022-11-24 | Nouryon Chemicals International B.V. | Polyester polyquats in cleaning applications |
US11596952B2 (en) | 2018-01-16 | 2023-03-07 | Clariant International Ltd | Esterquats for the flotation of non-sulfidic minerals and ores, and method |
CN113874118B (en) * | 2019-06-06 | 2024-04-23 | 巴斯夫欧洲公司 | Collector for flotation process |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE483525T1 (en) * | 2007-01-26 | 2010-10-15 | Cognis Ip Man Gmbh | METHOD FOR FLOTATION OF NON-SULFIDIC MINERALS AND ORES |
ES2568777T3 (en) * | 2010-01-08 | 2016-05-04 | Université De Lorraine | Flotation process to recover feldspar from a feldspar mineral |
CN102120196A (en) * | 2010-12-30 | 2011-07-13 | 中国铝业股份有限公司 | Method for adding collecting agent in process of floating bauxite |
WO2013092440A1 (en) * | 2011-12-19 | 2013-06-27 | Akzo Nobel Chemicals International B.V. | Compositions comprising polyester polyamine and polyester polyquaternary ammonium corrosion inhibitors and chelating agents |
EP2708282A1 (en) * | 2012-09-13 | 2014-03-19 | Clariant International Ltd. | Composition for dressing phosphate ore |
AU2013351085A1 (en) * | 2012-11-30 | 2015-05-07 | Akzo Nobel Chemicals International B.V. | Flotation of silicates from ores |
CN102941161B (en) * | 2012-12-05 | 2015-07-15 | 云南磷化集团科工贸有限公司 | Method for preparing flotation collecting agent by using swill-cooked dirty oil |
EP3208315A1 (en) * | 2016-02-16 | 2017-08-23 | Omya International AG | Process for manufacturing white pigment containing products |
EP3208314B1 (en) * | 2016-02-16 | 2018-08-15 | Omya International AG | Process for manufacturing white pigment containing products |
CN106269272B (en) * | 2016-10-13 | 2018-10-09 | 昆明冶金研究院 | A kind of preparation method of bauxite floatation desilication high-efficient collecting agent |
FR3070162B1 (en) | 2017-08-16 | 2019-08-16 | Arkema France | POLYESTERAMINES AND POLYESTERQUATS |
EP3444036A1 (en) | 2017-08-16 | 2019-02-20 | Omya International AG | Indirect flotation process for manufacturing white pigment containing products |
FR3092332B1 (en) | 2019-02-06 | 2021-01-08 | Arkema France | USE OF ESTERAMINE TO PREVENT AGGLOMERATION OF GAS HYDRATES |
CN111068925B (en) * | 2019-12-23 | 2020-10-16 | 中南大学 | Application of 2- (3-substituted ureido) -N-hydroxy-2-oxyacetonitride cyanide compounds in flotation |
CN111068924B (en) * | 2019-12-23 | 2020-10-16 | 中南大学 | Application of 2-cyano-N- (substituted carbamoyl) acetamide compound in flotation of calcium-containing minerals |
FR3119395B1 (en) | 2021-02-04 | 2022-12-16 | Arkema France | POLYESTERAMINES AND POLYESTERQUATS |
CN117206085B (en) * | 2023-11-07 | 2024-03-08 | 矿冶科技集团有限公司 | High-selectivity molybdenite flotation collector, and preparation method and application thereof |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2173909A (en) | 1937-06-28 | 1939-09-26 | Ninol Inc | Ore dressing |
US2389763A (en) * | 1941-04-24 | 1945-11-27 | Emulsol Corp | Separation of mineral values from ores |
US2398763A (en) | 1945-02-08 | 1946-04-23 | Leo M Fleming | Rotary cutter |
DE2547987A1 (en) | 1975-10-27 | 1977-04-28 | Henkel & Cie Gmbh | FLOTATIONAL COLLECTORS FOR SYLVIN |
WO1991001295A1 (en) | 1989-07-17 | 1991-02-07 | Henkel Kommanditgesellschaft Auf Aktien | Process for preparing quaternary ammonium compounds |
DE4016792A1 (en) | 1990-05-25 | 1991-11-28 | Henkel Kgaa | METHOD FOR OBTAINING MINERALS FROM NON-SULFIDIC ORES BY FLOTATION |
DE4026184A1 (en) | 1990-08-18 | 1992-02-20 | Henkel Kgaa | METHOD FOR REDUCING THE REMAINING FREE ALKYLATING AGENT IN AQUEOUS SOLUTIONS OF CATIONIC SURFACES |
DE4308792C1 (en) | 1993-03-18 | 1994-04-21 | Henkel Kgaa | Stabilised quaternised fatty acid tri:ethanolamine ester salt(s) prodn. - having stable colour and odour characteristics |
DE4409322C1 (en) | 1994-03-18 | 1995-04-06 | Henkel Kgaa | Process for the preparation of ester quats |
WO1997026995A1 (en) | 1996-01-26 | 1997-07-31 | Henkel Kommanditgesellschaft Auf Aktien | Biodegradable quaternary esters used as flotation aids |
EP0770594B1 (en) | 1995-10-26 | 1999-09-29 | Henkel Kommanditgesellschaft auf Aktien | Quaternary esters and their use for the preparation of surface active agents especially for hair and personal care |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE64275C (en) | L. J. ODELL in Chicago, County of Cook, State of Illinois, V. St. A | Type stick typewriter | ||
US2494132A (en) * | 1948-03-10 | 1950-01-10 | American Cyanamid Co | Beneficiation of acidic minerals |
US20050047983A1 (en) * | 2003-08-29 | 2005-03-03 | Cameron Tim B. | Ester quaternary cationic flotation collectors |
ATE483525T1 (en) * | 2007-01-26 | 2010-10-15 | Cognis Ip Man Gmbh | METHOD FOR FLOTATION OF NON-SULFIDIC MINERALS AND ORES |
ES2386978T3 (en) | 2007-03-02 | 2012-09-10 | Cognis Ip Management Gmbh | Polymeric esterquats with asymmetric side chains |
-
2007
- 2007-01-26 AT AT07001677T patent/ATE483525T1/en active IP Right Revival
- 2007-01-26 EP EP07001677.9A patent/EP1949963B2/en active Active
- 2007-01-26 ES ES07001677.9T patent/ES2354119T5/en active Active
- 2007-01-26 DE DE602007009632T patent/DE602007009632D1/en active Active
-
2008
- 2008-01-17 CA CA2676741A patent/CA2676741C/en active Active
- 2008-01-17 US US12/524,710 patent/US8474627B2/en not_active Ceased
- 2008-01-17 WO PCT/EP2008/000309 patent/WO2008089906A1/en active Application Filing
- 2008-01-17 US US14/790,635 patent/USRE46235E1/en active Active
-
2009
- 2009-08-24 NO NO20092889A patent/NO337171B1/en unknown
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2173909A (en) | 1937-06-28 | 1939-09-26 | Ninol Inc | Ore dressing |
US2389763A (en) * | 1941-04-24 | 1945-11-27 | Emulsol Corp | Separation of mineral values from ores |
US2398763A (en) | 1945-02-08 | 1946-04-23 | Leo M Fleming | Rotary cutter |
DE2547987A1 (en) | 1975-10-27 | 1977-04-28 | Henkel & Cie Gmbh | FLOTATIONAL COLLECTORS FOR SYLVIN |
WO1991001295A1 (en) | 1989-07-17 | 1991-02-07 | Henkel Kommanditgesellschaft Auf Aktien | Process for preparing quaternary ammonium compounds |
DE4016792A1 (en) | 1990-05-25 | 1991-11-28 | Henkel Kgaa | METHOD FOR OBTAINING MINERALS FROM NON-SULFIDIC ORES BY FLOTATION |
DE4026184A1 (en) | 1990-08-18 | 1992-02-20 | Henkel Kgaa | METHOD FOR REDUCING THE REMAINING FREE ALKYLATING AGENT IN AQUEOUS SOLUTIONS OF CATIONIC SURFACES |
DE4308792C1 (en) | 1993-03-18 | 1994-04-21 | Henkel Kgaa | Stabilised quaternised fatty acid tri:ethanolamine ester salt(s) prodn. - having stable colour and odour characteristics |
DE4409322C1 (en) | 1994-03-18 | 1995-04-06 | Henkel Kgaa | Process for the preparation of ester quats |
EP0770594B1 (en) | 1995-10-26 | 1999-09-29 | Henkel Kommanditgesellschaft auf Aktien | Quaternary esters and their use for the preparation of surface active agents especially for hair and personal care |
WO1997026995A1 (en) | 1996-01-26 | 1997-07-31 | Henkel Kommanditgesellschaft Auf Aktien | Biodegradable quaternary esters used as flotation aids |
Non-Patent Citations (6)
Title |
---|
"Separation and Purification Methods", 1973 |
"Solid/Liquid Separation Equipment Scale-up", 1977 |
B. WILLS, MINERAL PRO- CESSING TECHNOLOGY PLANT DESIGN, 1978 |
H. SCHUBERT, AUFBEREITUNG FESTER MINERALISCHER STOFFE, 1967 |
H. SCHUBERT, INT. J. MIN. PROC., vol. 9, 1982, pages 353 - 384 |
H. SCHUBERT: "Aufbereitung fester mineralischer Rohstoffe", 1977, pages: 310 - 311 |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011147855A2 (en) | 2010-05-28 | 2011-12-01 | Akzo Nobel Chemicals International B.V. | Quaternary ammonium compounds and their use as collectors in froth flotation processes |
WO2011147855A3 (en) * | 2010-05-28 | 2012-03-08 | Akzo Nobel Chemicals International B.V. | Use of quaternary ammonium compounds as collectors in froth flotation processes |
US8936159B2 (en) | 2010-05-28 | 2015-01-20 | Akzo Nobel Chemicals International B.V. | Use of quaternary ammonium compounds as collectors in froth flotation processes |
WO2012028542A1 (en) | 2010-08-30 | 2012-03-08 | Akzo Nobel Chemicals International B.V. | Use of polyester polyamine and polyester polyquaternary ammonium compounds as corrosion inhibitors |
US8940227B2 (en) | 2010-08-30 | 2015-01-27 | Akzo Nobel Chemical International B.V. | Use of polyester polyamine and polyester polyquaternary ammonium compounds as corrosion inhibitors |
US9228089B2 (en) | 2010-12-28 | 2016-01-05 | Akzo Nobel Chemicals International B.V. | Polyester polyamine and polyester polyquaternary ammonium corrosion inhibitors |
WO2015091308A1 (en) * | 2013-12-18 | 2015-06-25 | Akzo Nobel Chemicals International B.V. | Polyester polyquaternary ammonium compound collectors for reverse froth flotation of silicates from nonsulfidic ores |
EA031803B1 (en) * | 2013-12-18 | 2019-02-28 | Акцо Нобель Кемикалз Интернэшнл Б.В. | Polyester polyquaternary ammonium compound collector reagents for reverse froth flotation of silicates from nonsulfidic ores |
US10100146B2 (en) | 2013-12-18 | 2018-10-16 | Akzo Nobel Chemicals International, B.V. | Polyester polyquaternary ammonium compound collectors for reverse froth flotation of silicates from nonsulfidic ores |
WO2017141118A1 (en) * | 2016-02-16 | 2017-08-24 | Arkema France | Use of alkoxylated amines as collector agents for ore beneficiation |
WO2017141117A1 (en) * | 2016-02-16 | 2017-08-24 | Arkema France | Use of alkoxylated amines as collector agents for ore beneficiation |
FR3047674A1 (en) * | 2016-02-16 | 2017-08-18 | Ceca Sa | |
FR3047675A1 (en) * | 2016-02-16 | 2017-08-18 | Ceca Sa | |
US11648569B2 (en) | 2016-02-16 | 2023-05-16 | Arkema France | Use of alkoxylated amines as collector agents for ore beneficiation |
US10744517B2 (en) | 2016-02-16 | 2020-08-18 | Arkema France | Use of alkoxylated amines as collector agents for ore beneficiation |
US11596952B2 (en) | 2018-01-16 | 2023-03-07 | Clariant International Ltd | Esterquats for the flotation of non-sulfidic minerals and ores, and method |
US20210121894A1 (en) * | 2018-07-03 | 2021-04-29 | Nouryon Chemicals International B.V. | Collector composition containing biodegradable compound and process for treating siliceous ores |
WO2020007773A1 (en) | 2018-07-03 | 2020-01-09 | Nouryon Chemicals International B.V. | Collector composition containing biodegradable compound and process for treating siliceous ores |
CN113874118A (en) * | 2019-06-06 | 2021-12-31 | 巴斯夫欧洲公司 | Collectors for flotation processes |
CN113874118B (en) * | 2019-06-06 | 2024-04-23 | 巴斯夫欧洲公司 | Collector for flotation process |
CN110947519B (en) * | 2019-12-31 | 2021-10-26 | 天津天宝翔科技有限公司 | Silicate mineral inhibitor and preparation method and application thereof |
CN110947519A (en) * | 2019-12-31 | 2020-04-03 | 天津天宝翔科技有限公司 | Silicate mineral inhibitor and preparation method and application thereof |
WO2022243367A1 (en) | 2021-05-18 | 2022-11-24 | Nouryon Chemicals International B.V. | Polyester polyquats in cleaning applications |
Also Published As
Publication number | Publication date |
---|---|
CA2676741C (en) | 2016-08-30 |
DE602007009632D1 (en) | 2010-11-18 |
ES2354119T5 (en) | 2014-05-16 |
CA2676741A1 (en) | 2008-07-31 |
ATE483525T1 (en) | 2010-10-15 |
WO2008089906A8 (en) | 2008-12-11 |
NO20092889L (en) | 2009-08-25 |
NO337171B1 (en) | 2016-02-01 |
EP1949963B1 (en) | 2010-10-06 |
US8474627B2 (en) | 2013-07-02 |
ES2354119T3 (en) | 2011-03-10 |
USRE46235E1 (en) | 2016-12-13 |
EP1949963B2 (en) | 2014-04-02 |
US20100078364A1 (en) | 2010-04-01 |
WO2008089906A1 (en) | 2008-07-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1949963B1 (en) | Process for the flotation of non-sulfidic minerals and ores | |
EP1949964A1 (en) | Process for the flotation of non-sulfidic minerals and ores | |
EP2017009B1 (en) | Reverse iron ore flotation by collectors in aqueous nanoemulsion | |
AU708335B2 (en) | Biologically degradable esterquats as flotation aids | |
US9724706B2 (en) | Flotation of silicates from ores | |
AU636496B2 (en) | Froth flotation of silica or siliceous gangue | |
CA2787445C (en) | Flotation reagent for iron ores containing magnetite and/or haematite | |
US11596952B2 (en) | Esterquats for the flotation of non-sulfidic minerals and ores, and method | |
CA3079763C (en) | Esterquats for the flotation of non-sulfidic minerals and ores, and method | |
CA2244899A1 (en) | Biologically degradable esterquats as flotation aids | |
BR112020008741B1 (en) | STERQUATS FOR FLOTATION OF MINERALS AND NON-SULPHIDIUM ORE AND PROCESS | |
CA3188495A1 (en) | Method for flotation of a silicate-containing iron ore | |
CA3203534A1 (en) | Method for flotation of a silicate-containing iron ore |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20070126 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA HR MK RS |
|
17Q | First examination report despatched |
Effective date: 20090220 |
|
AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 602007009632 Country of ref document: DE Date of ref document: 20101118 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20101006 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Effective date: 20110228 |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20101006 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110206 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110207 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110106 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 |
|
26 | Opposition filed |
Opponent name: AKZO NOBEL CHEMICALS INTERNATIONAL B.V. Effective date: 20110628 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110131 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R026 Ref document number: 602007009632 Country of ref document: DE Effective date: 20110628 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110131 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110131 |
|
PGRI | Patent reinstated in contracting state [announced from national office to epo] |
Ref country code: AT Effective date: 20111003 |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110126 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110126 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 |
|
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
27A | Patent maintained in amended form |
Effective date: 20140402 |
|
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R102 Ref document number: 602007009632 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R102 Ref document number: 602007009632 Country of ref document: DE Effective date: 20140402 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: DC2A Ref document number: 2354119 Country of ref document: ES Kind code of ref document: T5 Effective date: 20140516 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101006 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140402 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 10 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20220118 Year of fee payment: 16 Ref country code: DE Payment date: 20220127 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20220126 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20230224 Year of fee payment: 17 Ref country code: AT Payment date: 20230118 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20230120 Year of fee payment: 17 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602007009632 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20230126 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230126 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230801 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230131 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20240209 Year of fee payment: 18 |